Agent for temporarily styling keratin-containing fibres containing a non-ionic starch modified by propylene oxide and a chitosane

ABSTRACT

Cosmetic agents for the temporary deformation of keratinic fibers which contain, in a cosmetic carrier, a combination of at least one chitosan compound and at least one nonionic starch modified by means of propylene oxide, produce a hairstyle with a high degree of hold, excellent flexibility, and good hair care.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of International ApplicationNo. PCT/EP2010/065860 filed 21 Oct. 2010, which claims priority toGerman Patent Application Nos. 10 2009 045 925.1 and 10 2009 045 933.2,both filed 22 Oct. 2009, each of which are incorporated herein byreference.

The present invention relates to cosmetic agents for temporarydeformation of keratinic fibers containing, in a cosmetic carrier, acombination of at least one chitosan compound and at least one nonionicstarch modified with propylene oxide.

Styling agents for deformation of keratinic fibers have been known forsome time and are used in various embodiments to build up, refresh, andfix in place hairstyles that, for many types of hair, can be obtainedonly using setting active substances. An important role is played byhair treatment agents used for permanent shaping and those used fortemporary shaping of the hair. Temporary shaping operations intended toyield good hold without impairing the healthy appearance of the hairsuch as its shine can be achieved, for example, using hair sprays, hairwaxes, hair gels, blow-dry waves, etc.

Corresponding agents for temporary shaping usually contain syntheticpolymers as a shaping component. Preparations having a dissolved ordispersed polymer can be applied onto hair using propellant gases or apump mechanism. Hair gels and hair waxes, however, are not applieddirectly onto the hair but instead distributed in the hair using a combor one's hands.

Synthetic polymers usually used in agents for temporary shaping aremanufactured from corresponding synthetically accessible monomers. Thesemonomers are obtained from fossil substances such as petroleum byconversion to the corresponding polymer modules, in some cases withexpenditure of energy.

In a more sustainable approach to nature as living space and toresources, it is still desirable to use for cosmetic products only thosecosmetic raw materials that are accessible, with as little energy use aspossible, from renewable raw materials. A reduction in the amount oreven a replacement of synthetic polymers can be undertaken, however,only when the substitute polymers exhibit the properties desired for theintended application and ensure that the keratin-containing fibers(e.g., hairstyle) are held in sufficiently stable fashion in the shapeimparted to them.

In addition, nature-based substitute polymers should impart volume tothe fiber collective and retain the elasticity and smoothness of thekeratin-containing fibers that are fixed as to shape. Formation onkeratin-containing fibers of polymer particles visible to the naked eyeshould be avoided. In addition, the keratin-containing fibers must notgive a dull impression, but should have a natural shine.

The present invention therefore provides a cosmetic composition thatbrings about very strong and durable shape retention, has a high volumeeffect, provides good fiber care, and does not exhibit the abovedisadvantages. A further intention is to be able to dispense,predominantly or as entirely as possible, with use of synthetic polymersbased on fossil raw materials.

A first subject of the invention is therefore a cosmetic agent fortemporary deformation of keratinic fibers, particularly human hair,containing, in a cosmetic carrier

-   -   at least one chitosan or derivative thereof, and    -   at least one nonionic starch modified by means of propylene        oxide.

“Keratinic fibers” according to the present invention refer to furs,wool, feathers, and particularly human hair.

Chitosans represent biopolymers and are hydrocolloids. In chemicalterms, they are partially deacetylated chitins of various molecularweights.

Manufacture of chitosans proceeds from chitin, preferably crustaceanshell residues, which are available in large quantities as cheap rawmaterials. The chitin is usually first deproteinated by addition ofbases, demineralized by adding mineral acids, and lastly deacetylated byadding strong bases. Molecular weights can be distributed over a broadspectrum. It is preferable to use those grades having an averagemolecular weight (weight average) from 800,000 to 1,200,000 Dalton, aviscosity per Brookfield (1-wt % in glycolic acid) 5000 mPa·s or less, adegree of deacetylation from 80 to 88%, and an ash content of 0.3 wt %or less.

Also appropriate as typical cationic biopolymers as chitosan derivativesare cationically derivatized chitosans (e.g., quaternization products)or alkoxylated chitosans.

Preferred agents include as a chitosan at least one neutralizationproduct of chitosan with at least one organic carboxylic acid, such asin particular formic acid, acetic acid, citric acid, lactic acid,pyrrolidonecarboxylic acid, tartaric acid, glycolic acid, nicotinicacid, hydroxyisobutyric acid, hydroxyisovaleric acid, or mixtures ofthese acids. Preferably, the organic carboxylic acid are chosen fromlactic acid, formic acid, pyrrolidonecarboxylic acid, nicotinic acid,hydroxyisobutyric acid, hydroxyisovaleric acid, or mixtures of theseacids. This neutralization product can be manufactured, for example, inan aqueous medium by adding chitosan and the corresponding organiccarboxylic acid.

Suitable chitosans are readily commercially available, for example,under the commercial designations Hydagen® CMF (1 wt % active substancein aqueous solution with 0.4 wt % glycolic acid, molecular weight500,000 to 5,000,000 g/mol, Cognis), Hydagen® HCMF (chitosan (80%deacetylated), molecular weight 50,000 to 1,000,000 g/mol, Cognis),Kytamer® PC (80 wt % active substance as chitosan pyrrolidonecarboxylate (INCI name: Chitosan PCA), Amerchol), and Chitolam® NB/101.

The chitosans orderivatives thereof are present in agents according tothe present invention preferably in an amount from 0.01 wt % to 5 wt %,more preferably 0.05 wt % to 2.0 wt %, very preferably 0.1 wt % to 1 wt%, based on weight of the agent according to the invention.

Starch is a reserve carbohydrate that is stored by many plants in theform of large starch grains (granules), usually 1 to 200 μm in size, invarious parts of the plant, for example, in tubers or roots, cerealseeds, fruits and in the pith. A nonionic starch modified with propyleneoxide that can be used according to the invention can be obtained fromthe starch of potatoes, corn, rice, peas, acorns, chestnuts, barley,wheat, bananas, sago, millet, sorghum, oats, barley, rye, beans, yams,arrowroot or cassava. Particularly pronounced effects according to thepresent invention are achieved with nonionic tapioca starch modifiedwith propylene oxide or nonionic potato starch modified with propyleneoxide or with mixtures of these two starches. Very particularlypreferably, the agent contains at least one nonionic potato starchmodified with propylene oxide.

Starch belongs to the homoglycan family and is a polycondensationproduct of D-glucose. Starch is made up of three structurally differentpolymers of d-glucopyranose, namely amylose, amylopectin, and anintermediate fraction. Higher plants contain 0 to 45 wt % amylose, basedon dry substance.

The intermediate fraction, also referred to as “anomalous amylopectin,”is structurally intermediate between amylose and amylopectin. Thequantitative indications defined in this Application for amylopectininclude the intermediate fraction.

It is preferred if the nonionic starch modified with propylene oxide hasan amylose content of 25 wt % or less, particularly 20 wt % or less,based on weight of the modified starch. It has become apparent that astarch having 17 to 22 wt % amylose and 78 to 83 wt % amylopectin isparticularly suitable for achieving the effect according to the presentinvention.

Amylose is made up of predominantly linear α-1,4-glycosidically linkedd-glucose, M_(r) 50,000 to 150,000. The resulting chains form doublehelices in the starch.

Amylopectin also contains, in addition to the α-1,4 links described foramylose, α-1,6 bonds (in an amount from 4 to 6%) as branching points.The average spacing between the branching points is equal toapproximately 12 to 17 glucose units. The molar mass of 10⁷ to 7* 10⁵corresponds to approx. 10⁵ glucose units, making amylopectin one of thelargest biopolymers. The branching points are distributed over themolecule in such a way that a bundle structure, with relatively shortside chains, develops. Each double helix is formed by two of these sidechains. As a result of the many branching points, amylopectin isrelatively easily soluble in water.

“Nonionic starch modified with propylene oxide” according to the presentinvention is a reaction product of a starch with propylene oxide. Areaction product of this kind includes at least one structural unit offormula (PS)

wherein at least one of R, R′, or R″ is a group of the formula

wherein n is greater than or equal to zero, and at most two of R, R′,and R″ is a hydrogen atom. In formulae of the Application, a bondidentified with the “*” symbol is a free valence of the correspondingstructural unit. Nonionic starches modified with propylene oxide areprovided, for example, by reacting a natural starch with propyleneoxide. Before modification with propylene oxide, the starch can havebeen exposed to a variety of physical or chemical processes such as heattreatment, shear, a thermal, acid-hydrolytic, oxidizing, or enzymaticcleavage, etc.

Preferably, the nonionic starch modified with propylene oxide is notpresent in the agent according to the present invention as individualstarch grains (granules). Accordingly, the starch grains aredisintegrated, for example, by heat or shear and the correspondingpolysaccharide molecules are released from the composite material. Thereleased polysaccharide molecules can be modified with propylene oxideafter or before release.

In a preferred embodiment, the nonionic starch modified with propyleneoxide is gelatinized. When an aqueous suspension of starch is heated orcompressed, a tangential swelling of the bodies is then observed at acritical temperature or pressure, with loss of birefringence, a changein X-ray structure, and an abrupt rise in the viscosity of the solution.This phenomenon is called “gelatinization.”

Nonionic starches according to the present invention modified withpropylene oxide are present in the agent in a molecular weightdistribution. Preferred nonionic starches modified with propylene oxidehave an average molecular weight from 50 to 2500 kDa (weight average).The molecular weight distribution is determined experimentally by gelfiltration chromatography against dextran. The weight average is anaverage molecular weight that takes into account the total weight of themolecules of various molecular weights, and not simply the number ofmolecules.

For statistical calculation of the weight average, firstly the “weightbreak” is defined:

w _(i)≦(n _(i) M _(i))/[Σ(N _(i) M _(i))].

This indicates the weight proportion, in the sample, of macromoleculesthat are made up of i segments (e.g. monomer modules) of mass M_(i) andthat occur Al_(i) times in the sample. The weight average of themolecular weight M_(w)=Σw_(i) M_(i) is thus given by

M _(w)=[Σ(N _(i)M² _(i))/[Σ(N _(i) M _(i))].

Particularly preferred agents contain nonionic starches modified withpropylene oxide having an average molecular weight (weight average) from100 to 2000 kDa, particularly 500 to 1800 kDa, very preferably from 700to 1000 kDa.

In order to adjust the molecular weight, the starch is subjected to amechanical and/or chemical treatment before or after modification withpropylene oxide. To elevate the molecular weight, the aforesaid starchcan be crosslinked. Crosslinking of the nonionic starch modified bymeans of propylene oxide exists when the linear or branchedpolysaccharide macromolecules of the starch are linked covalently bymeans of a crosslinking agent, forming a three-dimensional, insoluble,and still swellable polymeric network. Natural starch is generallyconsidered uncrosslinked, and, if crosslinking were desirable, requiresartificial crosslinking by means of synthesis chemistry. Artificialcrosslinking of this kind can be carried out using crosslinking agents.(Nonionic) starches (modified with propylene oxide) that do not exhibitsuch crosslinking are uncrosslinked.

Crosslinking occurs, for example, using the crosslinking agentepichlorohydrin. Here, a mixture (42-wt % in water) of starch modifiedwith propylene oxide is produced, into which mixture the desired amountof epichlorohydrin is stirred at room temperature. Once the targetviscosity is reached after a stirring time of 1 to 5 hours withviscosity monitoring, the crosslinked starch is isolated using ordinarymethods.

It is particularly preferred if agents according to the presentinvention contain at least one uncrosslinked nonionic starch modifiedwith propylene oxide as a modified nonionic starch.

To achieve a lower molecular weight from 100 to 400 kDa, the starchesare preferably exposed to mechanical cleavage, enzymatic cleavage(particularly using α-amylase, β-amylase, glucoamylase, or debranchingenzymes), acid-hydrolytic cleavage (particularly using hydrochloricacid, sulfuric acid, or phosphoric acid), thermal cleavage, or reactionwith oxidizing agents (such as periodate, hypochlorite, chromic acid,permanganate, nitrogen dioxide, hydrogen peroxide, or organicpercarboxylic acid, preferably with hydrogen peroxide). Kneaders,extruders, stator/rotor machines, and/or agitators are suitable formechanical cleavage of the starch.

Oxidative cleavage using hydrogen peroxide is preferred. Here, forexample, nonionic starch modified with propylene oxide is added towater, heated to 50 to 70° C., hydrogen peroxide is added, and stirringoccurs at 70 to 85° C. for 2 to 5 hours.

Propylene oxide content of the starch affects the fine-tuning of thehairstyle hold and hairstyle flexibility, as well as stability of thecosmetic agents. The parameters can be further optimized if the nonionicstarch modified with propylene oxide has, based on weight of themodified starch, a propylene oxide content from 1 to 20 wt %, morepreferably from 4 to 12 wt %, very preferably from 9.5 to 10.5 wt % orfrom 4.0 to 6.0 wt %. Propylene oxide content can be determined, forexample, by carrying out a Hodges cleavage using the method according toDIN EN 13268.

Cosmetic agents containing nonionic starches modified with propyleneoxide having, in a 43-wt % aqueous solution, a preferred viscosity from150 to 1,500,000 mP·s (Brookfield viscosimeter, spindle 7 at 20° C. and20 rpm) are outstandingly suitable for the invention. Particularlysuitable starches modified with propylene oxide have viscosities from10,000 to 200,000 mPa·s, more preferably from 25,000 to 180,000 mPa·s(measured under the conditions recited above).

It is preferred if the cosmetic agent contains the nonionic starchmodified with propylene oxide in an amount from 0.1 wt % to 10 wt %,more preferably from 0.2 wt % to 5.0 wt %, very preferably from 1.0 to3.0 wt %, based on weight of the agent.

Agents according to the present invention contain their activesubstances in a cosmetic carrier, preferably in a water-containingcosmetic carrier, an alcoholic cosmetic carrier, or an aqueous alcoholiccosmetic carrier. For temporary hair deformation, such carriers includelotions, water-in-oil emulsions, oil-in-water emulsions, creams, gels,foams, pomades, waxes, or other preparations that are suitable for useon the hair. It is preferred if the carrier is a water-containingcosmetic carrier or an aqueous alcoholic cosmetic carrier. It is if thecosmetic carrier of the agent according to the present inventioncontains at least 50 wt % water, based on the weight of the entireagent.

“Aqueous alcoholic” carriers for purposes of the present invention areaqueous compositions containing 3 to 70 wt % of a C₁ to C₄ alcohol,particularly ethanol or isopropanol. Agents according to the presentinvention can additionally contain further organic solvents such asmethoxybutanol, benzyl alcohol, ethyl diglycol, 1,2-propylene glycol, or1,3-propylene glycol. All water-soluble organic solvents are preferredin this context.

It is preferred if the agent according to the present inventionadditionally contains at least one film-forming and/or setting polymer.Additional film-forming and/or setting polymers of this embodiment aredifferent from the chitosan(s) (derivatives) and the nonionic starchmodified with propylene oxide. Film-forming and/or setting polymers canbe nonionically, anionically, amphoterically, or cationically charged,preferably nonionically or cationically charged.

“Polymers” according to the present invention are compounds constructedfrom a plurality of molecules wherein one type or several types of atomsor atom groupings (“constituent units,” “basic modules,” or “repeatingunits”) are repeatedly serially arranged, and that have a molecularweight of at least 10,000 g/mol. The polymers are obtained bypolyreaction, which can occur artificially (i.e., synthetically) ornaturally.

“Film-forming polymers” are those polymers that, upon drying, leavebehind a continuous film on the skin, hair, or nails. Film-formers ofthis kind can be used in a very wide variety of cosmetic products suchas face masks, make-up, hair setting agents, hair sprays, hair gels,hair waxes, hair therapies, shampoos, or nail polishes. Those polymershaving sufficient solubility in water, alcohol or in water/alcoholmixtures are particularly preferred. It is possible in this way toproduce corresponding solutions that can easily be utilized or furtherprocessed.

“Film-forming polymers” are also those polymers that, when applied in a0.01- to 20-wt % aqueous, alcoholic, or aqueous alcoholic solution, arecapable of depositing a transparent polymer film on the hair.

Setting polymers contribute to hold and/or buildup of hair volume andhair fullness of the overall hairstyle. These polymers are at the sametime also film-forming polymers and are therefore generally typicalsubstances for shape-imparting hair-treatment agents such as hairsetting agents, hair foams, hair waxes, and hair sprays. It is certainlypossible for film formation to be localized, and for only a few fibersto be connected to one another.

The additional film-forming and/or setting polymers are presentpreferably in an amount from 0.1 wt % to 10 wt %, particularly 1.0 wt %to 8.0 wt %, very preferably from 2.0 to 6.0 wt %, based on weight ofthe agent.

In a particularly preferred embodiment, agents according to the presentinvention contain at least one nonionic film-forming and/or nonionicsetting polymer as an additional film-forming and/or setting polymer.

The additional nonionic film-forming and/or nonionic setting polymersare present in the agent preferably in an amount from 0.1 wt % to 10 wt%, more preferably from 1.0 wt % to 8.0 wt %, very preferably from 2.0to 6.0 wt %, based on weight of the agent.

Nonionic film-forming and/or nonionic setting polymers are preferablychosen from at least one polymer of

-   -   homopolymers and nonionic copolymers of N-vinylpyrrolidone,    -   nonionic copolymers of isobutene,    -   nonionic copolymers of maleic acid anhydride.

Suitable polyvinylpyrrolidones include commercial products such asLuviskol® K 90 or Luviskol® K 85 of the BASF SE company.

Suitable polyvinyl acetate is marketed, for example, as an emulsionunder the trade name Vinac® by the Air Products company.

Agents having as a nonionic film-forming and/or nonionic setting polymerat least one polymer chosen from

-   -   copolymers of maleic acid anhydride and methyl vinyl ether,    -   polyvinylpyrrolidone,    -   copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic        acids having 2 to 18 carbon atoms, particularly        N-vinylpyrrolidone and vinyl acetate, or mixtures of these        polymers, are very particularly preferred according to the        present invention.

Those agents according to the present invention having as a nonionicfilm-forming and/or nonionic setting polymer at least one polymer chosenfrom

-   -   polyvinylpyrrolidone,    -   copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic        acids having 2 to 18 carbon atoms, particularly        N-vinylpyrrolidone and vinyl acetate,        or mixtures of these polymers, are in turn very particularly        preferred according to the present invention.

If copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acidshaving 2 to 18 carbon atoms, particularly N-vinylpyrrolidone and vinylacetate, are used, it is preferred if the molar ratio of the structuralunits of the polymer based on the N-vinylpyrrolidone monomer to thestructural units of the polymer based on the monomer that is vinylesters of carboxylic acids having 2 to 18 carbon atoms (particularlyvinyl acetate), is from 20:80 to 80:20, particularly 30:70 to 60:40.

Suitable copolymers of vinylpyrrolidone and vinyl acetate areobtainable, for example, under the trademark Luviskol® VA 37, Luviskol®VA 55, Luviskol® VA 64, and Luviskol® VA 73 from the BASF SE Company.

Agents according to the present invention preferably contain as anadditional film-forming and/or setting polymer, at least one cationicfilm-forming and/or cationic setting polymer. It is preferred accordingto the present invention if at least a combination of

-   -   at least one nonionic film-forming and/or nonionic setting        polymer and/or    -   at least one cationic film-forming and/or cationic setting        polymer        is present in the agent as an additional film forming and/or        setting polymer.

“Cationic polymers” are polymers having in the main chain and/or sidechain a group that can be “temporarily” or “permanently” cationic.According to the present invention, those polymers having a cationicgroup regardless of the pH of the agent are referred to as “permanentlycationic.” These are polymers having a quaternary nitrogen atom, forexample, in the form of an ammonium group. Preferred cationic groups arequaternary ammonium groups. Those polymers in which the quaternaryammonium group is bonded via a C1-4 hydrocarbon group to a main polymerchain constructed from acrylic acid, methacrylic acid, or derivativesthereof have proven particularly suitable.

A cationic film-forming and/or cationic setting polymer preferablysuitable according to the present invention is at least one cationicfilm-forming and/or cationic setting polymer that contains at least onestructural element of formula (M9) and additionally at least onestructural element of formula (M10)

wherein

-   R is a hydrogen atom or a methyl group,-   R′, R″ and R′″ are, mutually independently, a (C₁ to C₃₀) alkyl    group,-   X is an oxygen atom or an NH group,-   A is an ethane-1,2-diyl group or a propane-1,3-diyl group,-   n is 1 or 3.

All possible physiologically acceptable anions such as chloride,bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate,tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate,or p-toluenesulfonate, triflate, serve to compensate for the positivepolymer charge.

Such compounds are available, for example, as

-   -   copolymers of dimethylaminoethyl methacrylate, quaternized with        diethyl sulfate, with vinylpyrrolidone, having the INCI name        Polyquaternium-11, under the designations Gafquat® 440, Gafquat®        734, Gafquat® 755 (each ISP company) and Luviquat PQ 11 PN (BASF        SE),    -   copolymers of N-vinylpyrrolidone,        N-(3-dimethylaminopropyl)methacrylamide, and        3-(methacryloylamino)propyllauryldimethylammonium chloride (INCI        name: Polyquaternium-55), which is marketed e.g. under the        commercial name Styleze W 10 or Styleze W 20 (10 resp. 20 wt %        active substance in ethanol/water mixture) by the ISP company,    -   copolymers of N-vinylpyrrolidone, N-vinylcaprolactam,        N-(3-dimethylaminopropyl)methacrylamide, and        3-(methacryloylamino)propyllauryldimethylammonium chloride (INCI        name: Polyquaternium-69), which is marketed, for example, under        the commercial name AquaStyle® 300 (28 to 32 wt % active        substance in ethanol/water mixture) by the ISP company.

Cationic film-forming and/or cationic setting polymers are furtherselected from cationic quaternized cellulose derivatives.

Cationic quaternized cellulose derivatives are further suitable asfilm-forming and/or setting polymers.

Those cationic quaternized celluloses having more than one permanentcationic charge in a side chain are particularly advantageous forpurposes of the invention. Among these cationic celluloses, those havingthe INCI name Polyquaternium-4, marketed, for example, under thedesignations Celquat® H 100, Celquat® L 200 by the National StarchCompany are particularly suitable.

Further cationic polymers particularly preferred for use for theinvention are those cationic film-forming and/or cationic settingcopolymers having at least one structural element of formula (M11)

wherein R″ is a (C₁ to C₄) alkyl group, particularly a methyl group, andadditionally at least one further cationic and/or nonionic structuralelement.

All possible physiologically acceptable anions such as chloride,bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate,tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate,or p-toluenesulfonate, triflate, serve to compensate for the positivepolymer charge.

It is preferred if at least one copolymer (c1), having besides at leastone structural element of formula (M11) and additionally a structuralelement of formula (M6)

wherein R″ is a (C₁ to C₄) alkyl group, particularly a methyl group, ispresent as an additional cationic film-forming and/or cationic settingpolymer.

All possible physiologically acceptable anions such as chloride,bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate,tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate,or p-toluenesulfonate, triflate, serve to compensate for the positivepolymer charge of copolymers (c1).

Very particularly preferred cationic film-forming and/or cationicsetting polymers as copolymers (c1) contain 10 to 30 mol %, preferably15 to 25 mol %, and particularly 20 mol % structural units according toformula (M11), and 70 to 90 mol %, preferably 75 to 85 mol % andparticularly 80 mol % structural units according to formula (M6).

It is particularly preferred if copolymers (c1), in addition to polymerunits resulting from incorporation of structural units according toformulae (M11) and (M6) into the copolymer, a maximum of 5 wt %,preferably a maximum of 1 wt %, contain polymer units based on theincorporation of other monomers. Copolymers (c1) are preferablyconstructed exclusively from structural units of formula (M11), where R″=methyl, and (M6).

If a chloride ion is used to compensate for the positive charge of thepolymer, such N-methylvinylimidazole/vinylpyrrolidone copolymers arethen referred to according to INCI nomenclature as Polyquaternium-16 andare obtainable e.g. from BASF under the trade names Luviquat® Style,Luviquat® FC 370, Luviquat® FC 550, Luviquat® FC 905, and Luviquat® HM552.

If a methosulfate is used to compensate for the positive charge of thepolymer, such N-methylvinylimidazole/vinylpyrrolidone copolymers arethen referred to according to INCI nomenclature as Polyquaternium-44 andare obtainable e.g. from BASF under the trade names Luviquat® UltraCare.

In addition to or instead of copolymer or copolymers (c1), agentsaccording to the present invention can also contain copolymers (c2)that, proceeding from copolymer (c1), contain structural units offormula (M7) as additional structural units:

Further particularly preferred agents according to the present inventioncontain, as a cationic film-forming and/or cationic setting polymer, atleast one copolymer (c2) having at least one structural unit accordingto formula (M11-a), at least one structural unit according to formula(M6), and at least one structural unit according to formula (M7)

Here as well, it is particularly preferred if copolymers (c2), inaddition to polymer units resulting from incorporation of structuralunits according to formulae (M11-a), (M6), and (M7) into the copolymer,a maximum of 5 wt %, preferably a maximum of 1 wt %, contain polymerunits based on the incorporation of other monomers. Copolymers (c2) arepreferably constructed exclusively from structural units of formulae(M11-a), (M6), and (M7).

All possible physiologically acceptable anions such as chloride,bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate,tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate,or p-toluenesulfonate, triflate, serve to compensate for the positivepolymer charge of copolymers (c2).

If a methosulfate is used to compensate for the positive charge of thepolymer, such N-methylvinylimidazole/vinylpyrrolidone/vinylcaprolactamcopolymers are then referred to according to INCI nomenclature asPolyquaternium-46 and are obtainable, for example, from BASF under thetrade name Luviquat® Hold.

Very particularly preferred copolymers (c2) contain 1 to 20 mol %,preferably 5 to 15 mol %, and particularly 10 mol % structural unitsaccording to formula (M-11 a), and 30 to 50 mol %, preferably 35 to 45mol %, and particularly 40 mol % structural units according to formula(M6), and 40 to 60 mol %, preferably 45 to 55 mol %, and particularly 60mol % structural units according to formula (M7).

In addition to or instead of copolymer or copolymers (c1) and/or (c2),agents according to the present invention can also contain as a cationicfilm-forming and/or cationic setting polymer, copolymers (c3) having asstructural units structural units of formulas (M11-a) and (M6), as wellas further structural units from the group of the vinylimidazole unitsand from the group of the acrylamide and/or methacrylamide units.

Further particularly preferred agents according to the present inventioncontain, as an additional cationic film-forming and/or cationic settingpolymer, at least one copolymer (c3) that contains at least onestructural unit according to formula (M-11a), at least one structuralunit according to formula (M6), at least one structural unit accordingto formula (M10) and at least one structural unit according to formula(M12)

Here, it is particularly preferred if copolymers (c3) contain, besidespolymer units that result from incorporation of the aforesaid structuralunits in accordance with formulas (M11-a), (M6), (M8), and (M12) intothe copolymer, a maximum of 5 wt %, preferably a maximum of 1 wt %,polymer units based on incorporation of other monomers. Copolymers (c3)are preferably constructed exclusively from structural units of formulae(M11-a), (M6), (M8), and (M12).

All possible physiologically acceptable anions such as chloride,bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate,tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate,or p-toluenesulfonate, triflate, serve to compensate for the positivepolymer charge of component (c3).

If a methosulfate is used to compensate for the positive charge of thepolymer, suchN-methylvinylimidazole/vinylpyrrolidone/vinylimidazole/methacrylamidecopolymers are referred to according to INCI nomenclature asPolyquaternium-68 and are obtainable, for example, from BASF under thetrade name Luviquat® Supreme.

Very particularly preferred copolymers (c3) contain 1 to 12 mol %,preferably 3 to 9 mol %, and particularly 6 mol % structural unitsaccording to formula (M-11 a), and 45 to 65 mol %, preferably 50 to 60mol %, and particularly 55 mol % structural units according to formula(M6), and 1 to 20 mol %, preferably 5 to 15 mol %, and particularly 10mol % structural units according to formula (M8), and 20 to 40 mol %,preferably 25 to 35 mol %, and particularly 29 mol % structural unitsaccording to formula (M12).

Among the additional cationic film-forming and/or setting polymerschosen from cationic polymers having at least one structural element offormula (M11-a), those considered preferred are:

-   -   vinylpyrrolidone/1-vinyl-3-methyl-1H-imidazolium chloride        copolymers (such as the one having the INCI name        Polyquaternium-16 with the commercial designations Luviquat®        Style, Luviquat® FC 370, Luviquat® FC 550, Luviquat® FC 905, and        Luviquat® HM 552 (BASF SE)),    -   vinylpyrrolidone/1-vinyl-3-methyl-1H-imidazolium methyl sulfate        copolymers (such as the one having the INCI name        Polyquaternium-44 with the commercial designations Luviquat®        Care (BASF SE)),    -   vinylpyrrolidone/vinylcaprolactam/1-vinyl-3-methyl-1H-imidazolium        terpolymers (such as the one having the INCI name        Polyquaternium-46 with the commercial designations Luviquat®        Care or Luviquat® Hold (BASF SE)),    -   vinylpyrrolidone/methacrylamide/vinylimidazole/1-vinyl-3-methyl-1H-imidazolium        methyl sulfate copolymers (such as the one having the INCI name        Polyquaternium-68 with the commercial designation Luviquat®        Supreme (BASF SE)),        as well as mixtures of those polymers.

Further cationic polymers preferably usable in agents according to thepresent invention are “temporarily cationic” polymers. These polymersusually contain an amino group that is present at certain pH values as aquaternary ammonium group and therefore cationically.

Likewise considered preferably suitable as temporarily cationic polymersfor purposes of the invention are those having at least one structuralunit of formulae (M1-1) to (M1-8)

Those copolymers having at least one structural unit of formulae (M1-1)to (M1-8) and additionally at least one structural unit of formula (M10)

where n is 1 or 3 are preferred in this context.

The group of polymers

-   -   vinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl        methacrylate copolymer (for example, INCI name: Vinyl        Caprolactam/PVP/Di-methylaminoethyl Methacrylate Copolymer,        under the trade name Gaffix® VC 713 (ISP)),    -   vinylpyrrolidone/vinylcaprolactam/dimethylaminopropyl        methacrylamide copolymer (e.g. INCI name: VP/Vinyl        Caprolactam/DMAPA Acrylates Copolymer, under the trade name        Aquaflex® SF 40 (ISP)),    -   vinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl        methacrylate copolymer (for example, as 35 to 39% solids in        ethanol in the form of the commercial product Advantage LC E        having the INCI name: Vinyl Caprolactam/VP/Dimethylaminoethyl        Methacrylate Copolymer, Alcohol, Laurylpyrrolidone        (ISP)),vinylpyrrolidone/dimethylaminopropylmethacrylamide        copolymer (for example, INCI name: VP/DMAPA Acrylates Copolymer,        with the trade name Styleze CC-10 (ISP)),        is considered a preferred list for selection therefrom of at        least one or more polymers.

Cosmetic agents very particularly preferred according to the presentinvention conform to at least one of the following embodiments A) to O):

A): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid, and    -   at least one nonionic starch modified by means of propylene        oxide.

B): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid,    -   at least one nonionic starch modified by means of propylene        oxide, and    -   at least one nonionic film-forming and/or nonionic setting        polymer.

C): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid,    -   at least one nonionic starch modified by means of propylene        oxide, and    -   at least one nonionic film-forming and/or nonionic setting        polymer selected from the group that is constituted from        -   copolymers of maleic acid anhydride and methyl vinyl ether,        -   polyvinylpyrrolidone,        -   copolymers of N-vinylpyrrolidone and vinyl esters of            carboxylic acids having 2 to 18 carbon atoms, particularly            N-vinylpyrrolidone and vinyl acetate,            or mixtures of those polymers.

D): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid, and    -   at least one nonionic starch, modified by means of propylene        oxide and having a molecular weight (weight average) from 50 to        2500 kDa.

E): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid,    -   at least one nonionic starch, modified by means of propylene        oxide and having a molecular weight (weight average) from 50 to        2500 kDa, and    -   at least one nonionic film-forming and/or nonionic setting        polymer.

F): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid,    -   at least one nonionic starch, modified by means of propylene        oxide and having a molecular weight (weight average) from 50 to        2500 kDa, and    -   at least one nonionic film-forming and/or nonionic setting        polymer chosen        -   copolymers of maleic acid anhydride and methyl vinyl ether,        -   polyvinylpyrrolidone,        -   copolymers of N-vinylpyrrolidone and vinyl esters of            carboxylic acids having 2 to 18 carbon atoms, particularly            N-vinylpyrrolidone and vinyl acetate,            or mixtures of those polymers.

G): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid, and    -   at least one nonionic starch modified with propylene oxide and        having a viscosity in the range from 150 to 1,500,000 mPa·s,        preferably 10,000 to 200,000 mPa·s, more preferably from 25,000        to 180,000 mPa·s (based on a 43-wt % aqueous solution,        Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm).

H): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid,    -   at least one nonionic starch modified with propylene oxide and        having a viscosity in the range from 150 to 1,500,000 mPa·s,        preferably 10,000 to 200,000 mPa·s, particularly preferably from        25,000 to 180,000 mPa·s (based on a 43-wt % aqueous solution,        Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm), and    -   at least one nonionic film-forming and/or nonionic setting        polymer.

I): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid,    -   at least one nonionic starch modified with propylene oxide and        having a viscosity from 150 to 1,500,000 mPa·s, preferably        10,000 to 200,000 mPa·s, particularly preferably from 25,000 to        180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield        viscosimeter, spindle 7 at 20° C. and 20 rpm), and    -   at least one nonionic film-forming and/or nonionic setting        polymer chosen from        -   copolymers of maleic acid anhydride and methyl vinyl ether,        -   polyvinylpyrrolidone,        -   copolymers of N-vinylpyrrolidone and vinyl esters of            carboxylic acids having 2 to 18 carbon atoms, particularly            N-vinylpyrrolidone and vinyl acetate,            or mixtures of said polymers.

J): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid, and    -   at least one nonionic starch modified with propylene oxide and        having a molecular weight (weight average) from 50 to 2500 kDa        and a viscosity from 150 to 1,500,000 mPa·s, preferably 10,000        to 200,000 mPa·s, particularly preferably from 25,000 to 180,000        mPa·s (based on a 43-wt % aqueous solution, Brookfield        viscosimeter, spindle 7 at 20° C. and 20 rpm).

K): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid,    -   at least one nonionic starch modified with propylene oxide and        having a molecular weight (weight average) from 50 to 2500 kDa        and a viscosity from 150 to 1,500,000 mPa·s, preferably 10,000        to 200,000 mPa·s, particularly preferably from 25,000 to 180,000        mPa·s (based on a 43-wt % aqueous solution, Brookfield        viscosimeter, spindle 7 at 20° C. and 20 rpm), and    -   at least one nonionic film-forming and/or nonionic setting        polymer.

L): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid,    -   at least one nonionic starch modified with propylene oxide and        having a molecular weight (weight average) from 50 to 2500 kDa        and a viscosity from 150 to 1,500,000 mPa·s, preferably 10,000        to 200,000 mPa·s, particularly preferably from 25,000 to 180,000        mPa·s (based on a 43-wt % aqueous solution, Brookfield        viscosimeter, spindle 7 at 20° C. and 20 rpm), and    -   at least one nonionic film-forming and/or nonionic setting        polymer chosen from        -   copolymers of maleic acid anhydride and methyl vinyl ether,        -   polyvinylpyrrolidone,        -   copolymers of N-vinylpyrrolidone and vinyl esters of            carboxylic acids having 2 to 18 carbon atoms, particularly            N-vinylpyrrolidone and vinyl acetate,            or mixtures of those polymers.

M): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid, and    -   at least one nonionic starch modified with propylene oxide and        having a viscosity from 150 to 1,500,000 mPa·s, preferably        10,000 to 200,000 mPa·s, particularly preferably from 25,000 to        180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield        viscosimeter, spindle 7 at 20° C. and 20 rpm), and a propylene        oxide content from 1 to 20 wt %, preferably 4 to 12 wt %,        particularly preferably from 9.5 to 10.5 wt % or from 4.0 to 6.0        wt %, based on the weight of the modified starch.

N): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid,    -   at least one nonionic starch modified with propylene oxide and        having a viscosity from 150 to 1,500,000 mPa·s, preferably        10,000 to 200,000 mPa·s, particularly preferably from 25,000 to        180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield        viscosimeter, spindle 7 at 20° C. and 20 rpm), and a propylene        oxide content from 1 to 20 wt %, preferably 4 to 12 wt %,        particularly preferably from 9.5 to 10.5 wt % or from 4.0 to 6.0        wt %, based on the weight of the modified starch, and    -   at least one nonionic film-forming and/or nonionic setting        polymer.

0): A cosmetic agent for the temporary deformation of keratinic fibers,particularly human hair, containing, in a cosmetic carrier,

-   -   at least one neutralization product of chitosan with at least        one organic carboxylic acid,    -   at least one nonionic starch modified with propylene oxide and        having a viscosity from 150 to 1,500,000 mPa·s, preferably        10,000 to 200,000 mPa·s, particularly preferably from 25,000 to        180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield        viscosimeter, spindle 7 at 20° C. and 20 rpm), and a propylene        oxide content from 1 to 20 wt %, preferably 4 to 12 wt %,        particularly preferably from 9.5 to 10.5 wt % or from 4.0 to 6.0        wt %, based on the weight of the modified starch, and    -   at least one nonionic film-forming and/or nonionic setting        polymer chosen from        -   copolymers of maleic acid anhydride and methyl vinyl ether,        -   polyvinylpyrrolidone,        -   copolymers of N-vinylpyrrolidone and vinyl esters of            carboxylic acids having 2 to 18 carbon atoms, particularly            N-vinylpyrrolidone and vinyl acetate,            or mixtures of said polymers.

Preferred additional nonionic film-forming and/or nonionic settingpolymers of embodiments A) to O)—when listed—are polyvinylpyrrolidone,copolymers of N-vinylpyrrolidone and vinyl acetate, or mixtures thereof.

Preferred organic carboxylic acids of the neutralization product ofchitosan in accordance with embodiments A) to O) are chosen from lacticacid, formic acid, pyrrolidonecarboxylic acid, nicotinic acid,hydroxyisobutyric acid, hydroxyisovaleric acid, or mixtures of saidacids.

Preferred utilization quantities of the ingredients according toembodiments A) to O) are those recited previously (see above).

It is preferred to additionally use at least one nonionic surfactant.These surfactants can already, according to the present invention, havean emulsifying effect.

Nonionic surfactants contain as a hydrophilic group, for example, apolyol group, a polyalkylene glycol ether group, or a combination of apolyol and polyglycol ether group. Such compounds include:

-   -   addition products of 2 to 100 mol ethylene oxide and/or 1 to 5        mol propylene oxide with linear and branched fatty alcohols        having 8 to 30 carbon atoms, with fatty acids having 8 to 30        carbon atoms, and with alkylphenols having 8 to 15 carbon atoms        in the alkyl group,    -   addition products of 2 to 20 units of glycerol with linear or        branched fatty alcohols having 8 to 30 carbon atoms in the alkyl        group, with linear or branched fatty acids having 8 to 30 carbon        atoms in the alkyl group such as, the grades obtainable under        the marketing designations Dermofeel® G 10 LW (Straetmans        Chemical Products),    -   addition products, end-capped with a methyl or C₂ to C₆ alkyl        residue, of 2 to 50 mol ethylene oxide and/or 1 to 5 mol        propylene oxide with linear and branched fatty alcohols having 8        to 30 carbon atoms, with fatty acids having 8 to 30 carbon        atoms, and with alkylphenols having 8 to 15 carbon atoms in the        alkyl group, such as, for example, the grades obtainable under        the marketing designations Dehydol® LS, Dehydol® LT (Cognis),    -   C₁₂ to C₃₀ fatty acid mono- and diesters of addition products of        1 to 30 mol ethylene oxide with glycerol,    -   addition products of 5 to 60 mol ethylene oxide with castor oil        and hardened castor oil,    -   polyol fatty acid esters such as the commercial product Hydagen®        HSP (Cognis), or Sovermol® grades (Cognis),    -   alkoxylated triglycerides,    -   alkoxylated fatty acid alkyl esters of formula (E4-I)

R¹CO—(OCH₂CHR²)_(w)OR³   (E4-I),

wherein R¹CO is a linear or branched, saturated and/or unsaturated acylresidue having 6 to 22 carbon atoms, R² is hydrogen or methyl, R³ islinear or branched alkyl residues having 1 to 4 carbon atoms, and w is anumber from 1 to 20,

-   -   amine oxides,    -   hydroxy mixed ethers such as those described, for example, in        German Application 19738866,    -   sorbitan fatty acid esters and addition products of ethylene        oxide with sorbitan fatty acid esters, for example the        polysorbates,    -   sugar fatty acid esters and addition products of ethylene oxide        with sugar fatty acid esters,    -   addition products of ethylene oxide with fatty acid        alkanolamides and fatty amines,    -   sugar surfactants of the alkyl and alkenyl oligoglycoside types,        in accordance with formula (E4-II)

R⁴O-[G]_(p)   (E4-II),

-   -   wherein R⁴ is an alkyl or alkenyl residue having 4 to 22 carbon        atoms, G is a sugar residue having 5 or 6 carbon atoms, and p is        a number from 1 to 10. They can be obtained according to        relevant methods of preparative organic chemistry.

Particularly preferred for use in the agent according to the presentinvention are those nonionic surfactants chosen from

-   -   addition products of 2 to 20 units of glycerol with linear or        branched fatty alcohols having 8 to 30 carbon atoms in the alkyl        group,    -   addition products of 2 to 20 units of glycerol with linear or        branched fatty acids having 8 to 30 carbon atoms in the alkyl        group,    -   addition products of 5 to 60 mol ethylene oxide with castor oil        and hardened castor oil, and mixtures of the aforesaid        surfactants.

Nonionic surfactants are present in the agent preferably in an amountfrom 0.005 wt % to 10 wt %, particularly from 0.01 wt % to 2 wt %, basedon the weight of the agent according to the present invention.

The agent according to the present invention has acceptable hair-careproperties even without further care-providing substances. To enhancethe hair-care effect, the agent can additionally contain at least onecationic surfactant. Examples of cationic surfactants usable in theagents include quaternary ammonium compounds. Ammonium halides arepreferred, particularly chlorides and bromides, such asalkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, andtrialkylmethylammonium chlorides (e.g., cetyltrimethylammonium chloride,stearyltrimethylammonium chloride, distearyldimethylammonium chloride,lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride,and tricetylmethylammonium chloride). The highly biodegradablequaternary ester compounds called “esterquats,” such as themethylhydroxyalkyldialkoyloxyalkylammonium methosulfates marketed underthe trade names Dehyquart® and Stepantex®, can also be used.

Agents according to the present invention are preferably present asfoam. For that purpose, the agents are packaged in a delivery apparatusthat is either a pressurized-gas container additionally filled with apropellant (“aerosol container”) or a non-aerosol container.Pressurized-gas containers from which a product is distributed through avalve due to the internal gas pressure of the container are referred toas “aerosol containers.” A “non-aerosol container” is defined,conversely to the “aerosol” definition, as a vessel under standardpressure from which a product is distributed by mechanical action by wayof a pump system.

Agents according to the present invention are present particularlypreferably as aerosol hair foam in an aerosol container. The agenttherefore preferably additionally contains at least one propellant. Inthis connection, embodiments A) to O) are likewise considered, inparticular, as preferably suitable compositions packaged in an aerosolcontainer with at least one propellant for providing aerosol foam.

Agents according to the present invention that are present in the formof an aerosol product can be manufactured in usual fashion. Allconstituents of the agent except for the propellant are introduced intoa suitable pressure-tight container. The latter is then sealed with avalve. Lastly, the desired quantity of propellant is introduced usingconventional techniques.

As aerosol foam, propellants suitable according to the present inventioninclude N2O, dimethyl ether, CO2, air, alkanes having 3 to 5 carbonatoms such as propane, n-butane, isobutane, n-pentane, and isopentane,and mixtures thereof. In the embodiment as aerosol foam, the aforesaidalkanes, mixtures of the aforesaid alkanes, or mixtures of the aforesaidalkanes with dimethyl ether are used as the only propellant. Theinvention also expressly includes, however, the concurrent use offluorochlorocarbon propellants, particularly fluorocarbons.

Dimethyl ether, propane, n-butane, isobutane, and mixtures thereof arepreferred. Very particularly preferably, mixtures of propane and butaneare used as the only propellant at a weight ratio of propane to butanefrom 70:30 to 15:85. These mixtures are used in the agents preferably inan amount from 3 to 15 wt %, based on total weight of the agent.“Butane” according to the present invention is n-butane, isobutane, andmixtures of n-butane and isobutane. For a given spray apparatus, thesizes of the foam bubbles and the respective size distribution can beadjusted by the quantitative ratio between the propellant and the otherconstituents of the preparations.

When conventional aerosol containers are used, aerosol foam productscontain the propellant preferably in amounts from 1 to 35 wt %, based ontotal product. Quantities from 2 to 30 wt %, particularly 3 to 15 wt %,are particularly preferred.

Isopentane is preferably suitable as a propellant for foaming gel-typeagents in a two-chamber aerosol container, said propellant being isincorporated into the agents according to the present invention andbeing packaged in the first chamber of the two-chamber aerosolcontainer. Packaged in the second chamber of the two-chamber aerosolcontainer is at least one further propellant different from isopentanethat builds up in the two-chamber aerosol container a higher pressurethan isopentane. Propellants of the second chamber are preferably chosenfrom N2O, dimethyl ether, CO2, air, alkanes having 3 or 4 carbon atoms(such as propane, n-butane, isobutane), and mixtures thereof.

A second subject of the invention is the use of a cosmetic agent of thefirst subject of the invention for temporary deformation and/or shapefixing of keratinic fibers, particularly human hair.

A third subject of the invention is a method for temporary deformationof keratinic fibers, particularly human hair, wherein a cosmetic agentof the first subject of the invention is applied onto the keratinicfibers.

Preferably, the keratinic fibers, after application of the cosmeticagents of the first subject of the invention, are not rinsed and areleft on the fibers.

The Examples that follow are intended to explain the subject matter ofthe present invention without in any way limiting them.

EXAMPLES

The following formulation according to the present invention wasmanufactured in an aerosol container as an aerosol foam product:

Raw material I1 (wt %) Hydagen HCMF¹ 0.50 Lactic acid 0.28 Luviskol60/40 W NP² 10.70 Nonionic starch modified by means of propylene oxide³2.70 Sodium benzoate 0.30 D-Panthenol 0.15 Dow Corning 939⁴ 0.20Dehyquart A CA⁵ 1.00 Propane/butane 8.00 Water to 100 ¹Chitosan (80%deacetylated), molecular weight 50,000 to 1,000,000 g/mol, Cognis)²Copolymer of N-vinylpyrrolidone and vinyl acetate ³Potato starch,propylene oxide content: 10 wt % propylene oxide, viscosity: 64,000 mPa· s, average molecular weight (weight average): 800 kDa ⁴Approx. 32 to26% active substance, INCI name: Amodimethicone, Trideceth-12,Cetrimonium Chloride (Dow Corning) ⁵Trimethylhexadecylammonium chloride(approx. 24 to 26% active substance, INCI name: Aqua (Water),Cetrimonium Chloride) (Cognis)

Formulation I1 was applied onto a test subject as an aerosol foam inorder to fix the hairstyle as to shape. The hair achieved a naturalshine, a strong hairstyle hold, and durable volume.

1. Cosmetic agent for temporary deformation of keratinic fiberscomprising, in a cosmetic carrier: at least one chitosan or derivativethereof, and at least one nonionic starch modified with propylene oxide.2. Cosmetic agent according to claim 1, wherein the at least onechitosan or derivative thereof is a neutralization product of chitosanwith at least one organic carboxylic acid.
 3. Cosmetic agent accordingto claim 2, wherein the organic carboxylic acid is chosen from lacticacid, formic acid, pyrrolidonecarboxylic acid, nicotinic acid,hydroxyisobutyric acid, hydroxyisovaleric acid, and mixtures thereof. 4.Cosmetic agent according to claim 1, wherein the chitosan or derivativethereof is present in an amount from 0.01 wt % to 5 wt %, based on totalweight of the agent.
 5. Cosmetic agent according to claim 1, wherein themodified nonionic starch is a modified nonionic tapioca starch, amodified nonionic potato starch or a mixture thereof.
 6. Cosmetic agentaccording to claim 1, wherein the modified nonionic starch has anaverage molecular weight (weight average) from 50 to 2500 kDa. 7.Cosmetic agent according to claim 1, wherein the modified nonionicstarch has a propylene oxide content from 1 to 20 wt %, based on weightof the modified nonionic starch.
 8. Cosmetic agent according to claim 1,wherein the modified nonionic starch has, in a 43-wt % aqueous solution,a viscosity from 150 to 1,500,000 mPa·s, based on Brookfieldviscosimeter, spindle 7 at 20° C. and 20 rpm.
 9. Cosmetic agentaccording to claim 1, wherein the modified nonionic starch is present inan amount from 0.1 wt % to 10 wt %, based on total weight of the agent.10. Cosmetic agent according to claim 1, wherein the modified nonionicstarch is at least one uncrosslinked nonionic starch modified withpropylene oxide.
 11. Foam comprising the cosmetic agent according toclaim
 1. 12. Cosmetic agent according to claim 1 further comprising atleast one film-forming and/or setting polymer.
 13. Cosmetic agentaccording to claim 1 wherein the cosmetic carrier further comprises atleast 50 wt % water, based on total weight of the agent.
 14. Method fortemporary deformation of keratinic fibers comprising applying a cosmeticagent according to claim 1 onto the keratinic fibers.